JPH10312799A - Manufacture of nickel paste electrode for alkaline storage battery - Google Patents

Manufacture of nickel paste electrode for alkaline storage battery

Info

Publication number
JPH10312799A
JPH10312799A JP9136027A JP13602797A JPH10312799A JP H10312799 A JPH10312799 A JP H10312799A JP 9136027 A JP9136027 A JP 9136027A JP 13602797 A JP13602797 A JP 13602797A JP H10312799 A JPH10312799 A JP H10312799A
Authority
JP
Japan
Prior art keywords
powder
cobalt oxide
active material
paste
mixture
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
JP9136027A
Other languages
Japanese (ja)
Inventor
Takashi Eguro
高志 江黒
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Furukawa Battery Co Ltd
Original Assignee
Furukawa Battery Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Furukawa Battery Co Ltd filed Critical Furukawa Battery Co Ltd
Priority to JP9136027A priority Critical patent/JPH10312799A/en
Publication of JPH10312799A publication Critical patent/JPH10312799A/en
Pending legal-status Critical Current

Links

Classifications

    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

PROBLEM TO BE SOLVED: To attain the utilization factor and filled quantity of an active material equal to or higher than those in the past by applying the pulverizing/mixing process to the mixed powder of nickel hydroxide active material powder and cobalt oxide powder before a paste mixture is filled into an electrode substrate made of a porous sheet, and using a pulverizing/mixing machine. SOLUTION: The mixed powder of nickel hydroxide active material powder and cobalt oxide powder is put as a raw material into the dish-like mortar seat 1 of a fret mill A (pulverizing/mixing machine), then the pulverizing/mixing process for loosening the secondary coagulated body of the cobalt oxide in the mixed powder is applied via a motor 5 and rollers 9a, 9b. The mixed powder applied with the pulverizing/mixing process is kneaded together with a viscous liquid to form a pasty material, and it is filled into a porous electrode substrate. Even when the added quantity of the cobalt oxide is made smaller than before, the utilization factor and volume capacity density of the active material equal to or higher than those for the added quantity of 10% of the cobalt oxide required in the past can be attained, and the electrode can be economically manufactured.

Description

【発明の詳細な説明】DETAILED DESCRIPTION OF THE INVENTION

【０００１】[0001]

【発明の属する技術分野】本発明はアルカリ蓄電池用ペ
ースト式ニッケル極板の製造法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a paste-type nickel electrode plate for an alkaline storage battery.

【０００２】[0002]

【従来の技術】アルカリ蓄電池用ペースト式ニッケル極
板としては、電極基板として金属ニッケル粉末の焼結基
板を用い、その焼結基板の多孔内に化学的或いは電気化
学的に水酸化ニッケル活物質を充填する焼結式ニッケル
極板と、水酸化ニッケル活物質粉末を黒鉛粉やニッケル
粉末などの導電剤と混合し、その混合物粉体を穿孔薄板
より成るポケットに充填したポケット式ニッケル極板
や、ポリテトラフルオロエチレンなどの結着剤と導電剤
を共に粉末成形した水酸化ニッケル活物質を金属ネット
などの芯金に圧着したプラスチックボンド式ニッケル極
板などがあるが、特に近年の高容量化の要求に対応する
べく、水酸化ニッケル活物質の高密度充填が可能な、ス
ポンジ状ニッケルシートを電極基板とし、これに水酸化
ニッケル活物質を主体とし、これに増粘剤水溶液と導電
剤を添加、混合して成るペースト状の混合物粉体を充填
するペースト式ニッケル極板が提案され、実用化されて
いる。この場合、水酸化ニッケル活物質のみでは利用率
が低いので、ペースト式ニッケル極板の導電性を高める
ために、該ニッケル活物質粉末に、導電剤として一酸化
コバルト、水酸化コバルトなどのコバルト酸化物を添加
混合した混合物粉体を調製し、これをペースト状として
該多孔電極基板に充填してペースト式極板が製造されて
いる。該コバルト酸化物は、アルカリ電解液中で水酸化
物イオンに溶解し、極板をより貴な電位にすることで、
水酸化ニッケル活物質表面に析出し、導電性のあるコバ
ルト過酸化物膜を形成する。このコバルト過酸化物膜が
活物質全体に導電性網を形成することで活物質と集電体
との導電性を良好ならしめ、活物質利用率を向上させる
に役立つ。2. Description of the Related Art As a paste type nickel electrode plate for an alkaline storage battery, a metal nickel powder sintered substrate is used as an electrode substrate, and a nickel hydroxide active material is chemically or electrochemically applied to the pores of the sintered substrate. A pocket-type nickel electrode plate in which a sintered nickel electrode plate to be filled, a nickel hydroxide active material powder mixed with a conductive agent such as graphite powder or nickel powder, and the mixture powder filled into a pocket formed of a perforated thin plate; There is a plastic-bonded nickel electrode plate in which a nickel hydroxide active material formed by powder molding of a binder and a conductive agent such as polytetrafluoroethylene is pressed onto a metal core such as a metal net. In order to meet the demand, a sponge-like nickel sheet, which can be filled with nickel hydroxide active material at high density, is used as the electrode substrate, and the nickel hydroxide active material is mainly used for this. And then, this added aqueous thickener solution and the conductive agent, the paste type nickel electrode plate for filling a pasty mixture powder obtained by mixing have been proposed and put into practical use. In this case, since the utilization rate of the nickel hydroxide active material alone is low, in order to enhance the conductivity of the paste-type nickel electrode plate, the nickel active material powder is coated with a cobalt oxide such as cobalt monoxide or cobalt hydroxide as a conductive agent. A powdered mixture is prepared by adding and mixing a material, and the mixture is made into a paste and filled in the porous electrode substrate to produce a paste-type electrode plate. The cobalt oxide is dissolved in hydroxide ions in an alkaline electrolyte, and by making the electrode plate a more noble potential,
Deposits on the surface of the nickel hydroxide active material to form a conductive cobalt peroxide film. The cobalt peroxide film forms a conductive network over the entire active material, improves the conductivity between the active material and the current collector, and helps to improve the utilization rate of the active material.

【０００３】[0003]

【発明が解決しようとする課題】しかし乍ら、上記の従
来のニッケル活物質粉末にコバルト酸化物粉末を混入し
た混合物粉体のペースト状物を充填したペースト式ニッ
ケル極板において、焼結式ニッケル極板並みの活物質の
利用率８７〜８８％を得るためには、コバルト酸化物と
して例えば一酸化コバルトを用いた場合、約１０％もの
多量の添加量を必要とした。その結果、その多量の添加
により、それだけ水酸化ニッケル活物質の充填量が減っ
て電極容量が低下する不都合をもたらす。従って、より
少ないコバルト酸化物の添加量で約１０％の添加量と同
様股はそれ以上の活物質利用率が得られると共に、該活
物質の充填量を増大できるようにすることが望まれる。However, in the paste-type nickel electrode plate in which the paste-like material of the above-mentioned conventional nickel active material powder mixed with the cobalt oxide powder is filled, a sintered nickel electrode is used. In order to obtain a utilization rate of the active material of 87 to 88%, which is comparable to that of an electrode plate, when cobalt monoxide is used as the cobalt oxide, for example, a large addition amount of about 10% is required. As a result, the addition of a large amount thereof causes a disadvantage that the filling amount of the nickel hydroxide active material is reduced and the electrode capacity is reduced. Therefore, it is desired that the crotch can obtain an active material utilization rate higher than that of the addition amount of about 10% with a smaller addition amount of the cobalt oxide and increase the filling amount of the active material.

【０００４】[0004]

【課題を解決するための手段】本発明は、上記の課題を
解決したアルカリ蓄電池用ペースト式ニッケル極板の製
造法を提供するもので、水酸化ニッケル活物質粉末とコ
バルト酸化物粉末との混合物粉体に粉砕、混和処理を施
すことにより、コバルト酸化物の二次凝集体の凝集をほ
ぐすと共にほぐれたコバルト酸化物微粉末を該活物質粉
末中に均一に分散混和せしめた混合物粉体を調製した
後、この混合物を増粘剤及び溶媒と共に混練してペース
ト状とし、このペースト状物を多孔性シートから成る電
極基板に充填することを特徴とする。この場合、前記の
水酸化ニッケル活物質粉末とコバルト酸化物粉末との混
合物粉体に粉砕混和処理を施す工程は、粉砕混和機を用
いて行うことにより、コバルト酸化物粉末の二次凝集体
のほぐしとほぐされたコバルト酸化物微粉末を該活物質
粉末中に均一に分散混和せしめることができ好ましい。
また、該粉砕混和機は、水酸化ニッケル活物質粉末とコ
バルト酸化物粉末の混合物粉体を収容する皿状うす座
と、該皿状うす座の中心にその底板を貫通して垂直に取
り付けられた回転軸と、該回転軸に一体に取り付けられ
た固定保持部材と、該固定保持部材の左右に水平に配設
された一対のローラ支持軸と、該一対のローラ支持軸に
回転自在に且つ該皿状うす座の底面との間に僅かな間隙
を存して取り付けられた一対のローラと、該固定保持部
材の前後に水平に取り付けられた一対の羽根支持部材と
該一対の羽根支持部材の外端部に下端が該皿状うす座の
底面に摺接自在に取り付けられた一対の羽根板とから構
成されるフレットミルであるときは、コバルト酸化物粉
末の二次凝集体のほぐしとほぐされてコバルト酸化物微
粉末の該活物質粉末中への分散混和を繰り返し行うこと
ができ、充分良好に混和した混合物粉体が得られる。こ
の場合、該フレットミルの回転軸の回転速度は、５０ｒ
ｐｍ以下とすることにより、該一対のローラによる該混
合物中の水酸化ニッケル粉末の粒子を過度に微粉化する
ことが防止され、かさ密度の向上した混合物粉体をもた
らす。SUMMARY OF THE INVENTION The present invention provides a method for producing a paste-type nickel electrode plate for an alkaline storage battery, which solves the above-mentioned problems, and comprises a mixture of a nickel hydroxide active material powder and a cobalt oxide powder. By pulverizing and mixing the powder, the coagulation of the secondary agglomerate of the cobalt oxide is loosened, and the loosened cobalt oxide fine powder is uniformly dispersed and mixed in the active material powder to prepare a mixed powder. After that, the mixture is kneaded with a thickener and a solvent to form a paste, and the paste is filled in an electrode substrate formed of a porous sheet. In this case, the step of pulverizing and mixing the mixture powder of the nickel hydroxide active material powder and the cobalt oxide powder is performed by using a pulverizer and a pulverizer, thereby forming a secondary aggregate of the cobalt oxide powder. It is preferable that the loosened cobalt oxide fine powder can be uniformly dispersed and mixed in the active material powder.
Further, the pulverizer is mounted vertically on a dish-shaped bell seat for accommodating a powder mixture of nickel hydroxide active material powder and cobalt oxide powder, and through the bottom plate at the center of the dish-shaped bell seat. Rotating shaft, a fixed holding member integrally attached to the rotating shaft, a pair of roller support shafts horizontally disposed on the left and right of the fixed holding member, and rotatably on the pair of roller support shafts and A pair of rollers mounted with a slight gap between the bottom surface of the dish-shaped seat, a pair of blade support members mounted horizontally before and after the fixed holding member, and the pair of blade support members When the fret mill is composed of a pair of blades, the lower end of which is slidably attached to the bottom surface of the dish-shaped conifer at the outer end of the fret mill, the secondary aggregate of the cobalt oxide powder is loosened. The active material powder of unraveled cobalt oxide fine powder Can be repeated a dispersion admixture into the mixture powder obtained was thoroughly well mixed. In this case, the rotation speed of the rotation shaft of the fret mill is 50r
pm or less prevents the particles of the nickel hydroxide powder in the mixture from being excessively pulverized by the pair of rollers, resulting in a mixture powder having an improved bulk density.

【０００５】[0005]

【発明の実施の形態】従来、活物質の利用率の向上のた
め水酸化ニッケル粉末に添加されるコバルト酸化物粉末
は、単に混合機により水酸化ニッケル粉末と混合し、８
７〜８８％の利用率の向上をもたらすには、水酸化ニッ
ケル活物質に対し約１０重量％の多量の添加を必要とし
ていた。本願の発明者は、その原因を追究してみた所、
その原因は、コバルト酸化物粉末は凝集性が強く、平均
粒径数ミクロン程度の一次粒子が互いに凝集し易く、そ
の大部分が平均粒径０．１ｍｍ〜０．５ｍｍ程度の二次
凝集体となる傾向が強いので、これを水酸化ニッケル粉
末に混合し、その混合物粉体を混合機で混合しても、コ
バルト酸化物粉末の一部は二次凝集体のまゝで水酸化ニ
ッケル粉末中に混合されるので、その分散性は悪く、そ
の結果、上記のように約１０％程度多量に添加しなけれ
ば活物質利用率が８７〜８８％に向上しないものと思わ
れる。また、その後、この混合物粉体を、混練機によ
り、増粘剤と溶媒と共に、例えば、カルボキシメチルセ
ルロース（ＣＭＣ）と水と共に混練してペースト状とす
るのであるが、そのペーストの粘度は、一般に、該多孔
性基板に充填するに適した１０〜２０Ｐａ・ｓ以下と低
くするため、混練機で混練しても該コバルト酸化物粉末
の二次凝集体に充分な剪断応力をかけることができず、
従って、電極基板に充填されるペースト混合物中には、
コバルト酸化物粉末の凝集体のまゝ残ってしまうので、
活物質利用率は８７〜８８％以上に向上しないことが判
った。そこで発明者は、上記の事実に注目し、該活物質
粉末中へのコバルト酸化物粉末の添加量を少なくしても
従来の添加量の場合に得られる活物質利用率と同等又は
それ以上の活物質利用率をもたらし、経済的で且つ高容
量のペースト式ニッケル極板を得るため、鋭意研究を重
ねた結果、水酸化ニッケルとコバルト酸化物との混合物
粉体をペースト状とする以前に、粉砕混和機にかけ、粉
砕混和処理を施すようにし、これによりコバルト酸化物
粉末の二次凝集体をほぐし、一次粒子から成るほぐれた
コバルト酸化物微粒子とすると共に、その微粒子の粉末
を該水酸化ニッケル粉末中に均一に分散混和させた混合
物粉体に調製するという事前処理を行うことにより、次
でこの調製混合物粉体を、従来と同様に該混練機により
所定量の増粘剤及び溶媒と共に混練してペーストとし、
これを多孔電極基板に、例えばスポンジ状ニッケルシー
トに充填することで、上記の課題を解決することができ
た。従って、従来よりも少ないコバルト酸化物粉末の添
加量で従来と略同等又はそれ以上の活物質利用率をもた
らすペースト式ニッケル極板が得られ、また従来と同じ
添加量の場合は、活物質利用率が従来に比し著しく向上
するペースト式ニッケル極板が得られる効果をもたらし
た。従って、またそのコバルト酸化物粉末の添加量を少
なくした分を水酸化ニッケル活物質の添加量を増大でき
るので、容量密度の増大したペースト式ニッケル極板が
得られる等の効果をもたらす。DESCRIPTION OF THE PREFERRED EMBODIMENTS Conventionally, a cobalt oxide powder added to a nickel hydroxide powder for improving the utilization rate of an active material is simply mixed with the nickel hydroxide powder by a mixer to form a powder.
A 7-88% improvement in utilization required a large addition of about 10% by weight to the nickel hydroxide active material. The inventor of the present application has investigated the cause,
The cause is that the cobalt oxide powder has strong agglomeration properties, primary particles having an average particle size of about several microns are easily aggregated with each other, and most of them are secondary aggregates having an average particle size of about 0.1 mm to 0.5 mm. Therefore, even if this is mixed with nickel hydroxide powder and the mixture powder is mixed with a mixer, a part of the cobalt oxide powder remains in the form of secondary aggregates in the nickel hydroxide powder. , The dispersibility is poor. As a result, it is considered that the active material utilization rate does not improve to 87 to 88% unless about 10% is added in a large amount as described above. After that, the mixture powder is kneaded with a kneader together with a thickener and a solvent, for example, with carboxymethylcellulose (CMC) and water to form a paste. The viscosity of the paste is generally In order to reduce the pressure to 10-20 Pa · s or less suitable for filling the porous substrate, it is not possible to apply sufficient shear stress to the secondary aggregate of the cobalt oxide powder even if kneaded with a kneader,
Therefore, in the paste mixture filled in the electrode substrate,
Since the aggregates of the cobalt oxide powder remain,
It was found that the active material utilization did not increase to 87-88% or more. Therefore, the inventor pays attention to the above fact, and even if the addition amount of the cobalt oxide powder in the active material powder is reduced, the utilization ratio of the active material obtained in the case of the conventional addition amount is equal to or more than that. As a result of intensive research to provide an active material utilization rate and obtain an economical and high-capacity paste-type nickel electrode plate, before the mixture powder of nickel hydroxide and cobalt oxide was formed into a paste, In a pulverizing mixer, a pulverizing and mixing treatment is performed, whereby the secondary aggregates of the cobalt oxide powder are loosened to obtain loose cobalt oxide fine particles composed of primary particles, and the fine particle powder is mixed with the nickel hydroxide. By performing a pretreatment of preparing a mixture powder uniformly dispersed and mixed in the powder, the prepared mixture powder is then subjected to a predetermined amount of a thickener and a solvent using the kneading machine in the same manner as before. Both kneaded to a paste,
By filling this into a porous electrode substrate, for example, a sponge-like nickel sheet, the above-mentioned problem could be solved. Therefore, it is possible to obtain a paste-type nickel electrode plate that provides an active material utilization rate substantially equal to or higher than the conventional one with the addition amount of the cobalt oxide powder smaller than the conventional one. This has the effect of obtaining a paste-type nickel electrode plate in which the rate is significantly improved as compared with the conventional case. Therefore, the addition amount of the nickel hydroxide active material can be increased by reducing the addition amount of the cobalt oxide powder, so that a paste-type nickel electrode plate having an increased capacity density can be obtained.

【０００６】このようなニッケル水酸化物粉末と二次凝
集体を不可避に含むコバルト酸化物粉末との混合物粉体
の粉砕混和処理工程には、クラッシャーの一種である粉
砕混和機を用いることが好ましい。その粉砕混和機とし
て、いわゆるフレット（ｅｄｇｅ ｒｕｎｎｅｒ ｍｉ
ｌｌ）を用いることが好ましい。その１例を添付図面の
図１〜図４に示す。図１〜図３は、本発明に用いる粉砕
混和機Ａの１例のフレットミルを示す。該フレットミル
Ａは、次のような構成を有する。即ち、図面で１は、円
形底板１ａとその外周の所定の高さから成る円形周側壁
１ｂとから成る鋼製の円形皿状うす座、２は、該皿状う
す座１の底板１ａの中心を貫通し垂直方向に延びロール
ベアリング２ａを介して該底板１ｂに回転自在に取り付
けられた回転軸、該回転軸２は、その下端部に取り付け
られたプーリ３及びベルト４を介して連結するモータ５
により所望の回転速度で回転せしめられる。６は、該回
転軸２の上端膨出部外周に下端面に形成した嵌合用凹部
６ａで嵌合され、且つ頂面から挿通されたボルト７によ
り該回転軸２に一体に結着固定されて該回転軸２と共に
回転する筒状の鋼製の固定保持部材、８ａ，８ｂは、該
固定保持部材６の左右に水平に一体に配設した一対のロ
ーラ支持軸、９ａ，９ｂは、夫々のローラ支持軸８ａ，
８ｂにボールベヤリング１０ａ，１０ｂを介して回転自
在に且つ該皿状うす座１の底板１ａの上面との間に僅か
な数ミリの間隙ｇ，ｇを有して取り付けられたローラを
示す。該ローラ９ａ，９ｂは、該回転軸２の回転と共に
回転せしめられる。１１ａ，１１ｂは、該固定支持部材
６の前後に、即ち、前記のローラ支持軸８ａ，８ｂに対
し直角の回転角度位置に水平に延設した一対の鋼製の羽
根支持部材、１２ａ，１２ｂは、夫々の羽根支持部材１
１ａ，１１ｂの外端部に取り付けられた下端が該皿状う
す座１の底板１ａ上面、即ち、うす座に摺接自在に垂直
方向に立てて取り付けられた一対の羽根板を示す。尚、
図示の羽根支持部材１１ａ，１１ｂは、内端部で該固定
保持部材６の周面に溶接により取り付けられ、外端部は
下向きに下垂して折り曲げられ、その下垂端部にボルト
締めなどの結着手段１３により羽根板１２ａ，１２ｂを
取り付けたものである。１４は、床面Ｂに固設された支
持基台を示し、該皿状うす座１を下面から四本の支柱１
４ａにより該支持基台１４を所定の高さに支持する。[0006] In the step of pulverizing and mixing such a mixture of nickel hydroxide powder and cobalt oxide powder inevitably containing secondary aggregates, it is preferable to use a pulverizing mixer as a kind of crusher. . A so-called frette (edge runner mi) is used as the pulverizer.
It is preferred to use II). One example is shown in FIGS. 1 to 3 show a fret mill as an example of the pulverizer A used in the present invention. The fret mill A has the following configuration. That is, in the drawing, 1 is a steel circular dish-shaped seat composed of a circular bottom plate 1a and a circular peripheral side wall 1b having a predetermined height on the outer periphery, and 2 is a center of the bottom plate 1a of the dish-shaped thin seat 1. , A rotating shaft extending vertically and rotatably attached to the bottom plate 1b via a roll bearing 2a, and a motor connected to the rotating shaft 2 via a pulley 3 and a belt 4 attached to its lower end. 5
, Thereby rotating at a desired rotation speed. 6 is fitted to the outer periphery of the upper end bulging portion of the rotating shaft 2 by a fitting concave portion 6a formed in the lower end surface, and is integrally fixed to the rotating shaft 2 by a bolt 7 inserted from the top surface. A cylindrical steel fixed holding member 8a, 8b that rotates together with the rotary shaft 2 is a pair of roller support shafts horizontally and integrally disposed on the left and right sides of the fixed holding member 6, and 9a, 9b is a respective one. Roller support shaft 8a,
Reference numeral 8b denotes a roller rotatably mounted via the ball bearings 10a and 10b and having gaps g of a few millimeters between the upper surface of the bottom plate 1a of the dish-shaped seat 1 and a roller g. The rollers 9a and 9b are rotated together with the rotation of the rotating shaft 2. 11a and 11b are a pair of steel blade support members extending horizontally before and after the fixed support member 6, that is, at a rotation angle position perpendicular to the roller support shafts 8a and 8b. , Each blade support member 1
The lower ends attached to the outer ends of 1a and 11b indicate the upper surface of the bottom plate 1a of the dish-shaped seat 1, that is, a pair of blade plates which are vertically slidably attached to the seat. still,
The illustrated blade supporting members 11a and 11b are attached to the peripheral surface of the fixed holding member 6 by welding at the inner ends, and are bent downward at the outer ends, and are connected to the hanging ends by bolting or the like. The blades 12a and 12b are attached by attaching means 13. Reference numeral 14 denotes a support base fixed to the floor B, and the plate-shaped seat 1 is provided with four columns 1
4a, the support base 14 is supported at a predetermined height.

【０００７】上記のように構成したフレットミルＡの作
動は次の通りである。該皿状うす座１に、原料として活
物質ニッケル水酸化物粉末に凝集体を含むコバルト酸化
物粉末を該ニッケル水酸化物粉末に対し所定量混入して
成る混合粉体ａを投入し、該モータ５を駆動し、該回転
軸２を所定の回転速度で矢示の方向に回転させると、こ
れに伴い一対の該ローラ９ａ，９ｂは矢示方向に回転
し、このローラ９ａ，９ｂにより、これらローラ９ａ，
９ｂと皿状うす座１の底板１ａ上面との間隙ｇに入り込
んだ混合粉体ａをその上面から加圧し、その混合粉体中
のコバルト酸化物の二次凝集体をほぐす粉砕作用を行
う、次で、その夫々のローラ９ａ，９ｂの後方の該羽根
板１２ａ，１２ｂは該皿状うす座１の底板１ａ上面に摺
接し乍ら矢示方向に回転し、夫々の前方のローラ９ａ，
９ｂで該皿状うす座１の底板１ａに押圧された層状の混
合物粉ａを掻き取り乍ら混和作用を行う。この混和作用
により、ほぐされたコバルト酸化物微粉末を該水酸化ニ
ッケル粉末中に分散混和せしめられる。かくして、該回
転軸２の１回転により該混合物粉体ａに対し、該ローラ
９ａによる粉砕ほぐし作用と次で該羽根板１２ａによる
混和作用と次で該ローラ９ｂによる粉砕作用と次で該羽
根板１２ｂによる混和作用が交互に繰り返される。而し
て、所要時間、該回転軸２を所定の回転速度で所望数回
転させ、上記の粉砕混和作用を多数回繰り返し、かくし
て、遂には、原料中に含有する二次凝集体の殆ど全てが
充分にほぐれた実質上一次粒子から成るコバルト酸化物
微粉末が、該水酸化ニッケル活物質中に均一に分散混在
した良好な混合物粉体が調製される。The operation of the fret mill A configured as described above is as follows. A mixed powder a obtained by mixing a predetermined amount of an active material nickel hydroxide powder and a cobalt oxide powder containing an agglomerate with the nickel hydroxide powder is introduced into the dish-shaped Taurus 1, When the motor 5 is driven to rotate the rotating shaft 2 at a predetermined rotational speed in the direction indicated by the arrow, a pair of the rollers 9a and 9b rotate in the direction indicated by the arrow, and the rollers 9a and 9b These rollers 9a,
9b and the mixed powder a which has entered the gap g between the upper surface of the bottom plate 1a of the dish-shaped constellation 1 is pressed from the upper surface thereof to perform a pulverizing action to loosen secondary aggregates of cobalt oxide in the mixed powder. Next, the blades 12a and 12b behind the respective rollers 9a and 9b rotate in the direction indicated by the arrow while sliding on the upper surface of the bottom plate 1a of the dish-shaped seat 1, and the respective forward rollers 9a and 9b rotate.
In 9b, the mixing action is carried out while scraping off the layered mixture powder a pressed on the bottom plate 1a of the dish-shaped seat 1. By this mixing action, the loosened cobalt oxide fine powder is dispersed and mixed in the nickel hydroxide powder. Thus, by one rotation of the rotary shaft 2, the mixture powder a is pulverized by the rollers 9a, then mixed by the blades 12a, then pulverized by the rollers 9b, and then the blades. The mixing action by 12b is alternately repeated. Thus, the required number of rotations of the rotating shaft 2 at a predetermined rotation speed for a required time, and the above-mentioned pulverization-mixing action is repeated many times, so that almost all of the secondary aggregates contained in the raw material finally become A good mixture powder is prepared in which the cobalt oxide fine powder substantially consisting of primary particles that has been sufficiently loosened is uniformly dispersed and mixed in the nickel hydroxide active material.

【０００８】尚、図示のように、該一対の羽根支持部材
１１ａ，１１ｂを、長杆と短杆とすると共に、その夫々
の羽根支持部材１１ａ，１１ｂをその夫々の水平板部１
１ａ１，１１ｂ１に対しその外端部１１ａ２，１１ｂ２
を斜めに折り曲げてねじれた垂直板部となし、その夫々
の斜めにねじれた垂直板部１１ａ２，１１ｂ２に取り付
けた羽根板１２ａ，１２ｂが夫々の羽根板１２ａ，１２
ｂを該ローラ９ａ，９ｂの軌道から外側及び内側にはみ
出した混合物粉体をローラの該軌道内に戻すようにその
面が斜めに向くように傾斜させて取り付けることが好ま
しい。これにより、混合物粉体を該ローラ９ａ，９ｂの
軌道からはずれることなく、その全てを確実に粉砕混和
処理できる。尚、該一対の羽根支持部材１１ａ，１１ｂ
の断面形状や長さ、これに取り付けられる一対の羽根板
の位置や傾斜角度などは、所望に応じ適宜の手段で変え
ることができ、必要に応じ、調節自在に取り付けられる
ように設計することができる。尚、上記フレットミルの
動作中は、粉が多少舞うので、通常、皿状うす座１の上
部にはローラ９ａ，９ｂ等をすっぽり覆うカバーが施さ
れるが、図面ではこれを省略した。As shown in the figure, the pair of blade supporting members 11a and 11b are long and short rods, and the respective blade supporting members 11a and 11b are respectively connected to the respective horizontal plate portions 1.
1a1, 11b1 and outer ends 11a2, 11b2 thereof
Is bent obliquely to form a twisted vertical plate portion, and the blade plates 12a, 12b attached to the respective obliquely twisted vertical plate portions 11a2, 11b2 are provided with the respective blade plates 12a, 12b.
It is preferable that the mixture powder b protrudes from the tracks of the rollers 9a and 9b to the outside and the inside, and is mounted so as to be inclined so that the surface thereof is inclined so as to return the mixed powder to the rollers. As a result, all of the mixture powder can be reliably ground and mixed without deviating from the trajectories of the rollers 9a and 9b. The pair of blade support members 11a, 11b
The cross-sectional shape and length of the blade, the position and the inclination angle of the pair of blades attached to it can be changed by appropriate means as desired, and can be designed so that they can be adjusted as needed. it can. During the operation of the fret mill, a small amount of powder flutters. Therefore, a cover that completely covers the rollers 9a and 9b and the like is usually provided on the upper part of the dish-shaped seat 1, but this is omitted in the drawings.

【０００９】該回転軸２の回転速度は、遅いほど該混合
物粉末に対する押圧力は減少し、ローラの大きさや重量
にもよるが、特に、以下の実施例に明らかにするよう
に、５０ｒｐｍ以下の低速で回転させることが好まし
い。これにより、二次凝集していない水酸化ニッケルの
一次粒子を過度に粉砕し、その過度の微粉化による活物
質の電極基板への充填性を悪くし、活物質のロスを生じ
たり、ローラと粉末の摩擦による発熱が大きくなり、水
酸化ニッケルの変質をもたらし、過電極性能の低下をも
たらすなどの悪影響を未然に防止でき、かくして、調製
した混合物粉体は、かさ密度が増大し、これをペースト
として多孔性電極基板へ充填するときの充填性を向上
し、充填にロスのない而も容量密度の増大した高性能の
ペースト式ニッケル極板を製造することができる。As the rotation speed of the rotating shaft 2 decreases, the pressing force against the mixture powder decreases as the rotation speed decreases, and it depends on the size and weight of the roller. In particular, as will be apparent from the following examples, the rotation speed is not more than 50 rpm. It is preferable to rotate at low speed. As a result, the primary particles of nickel hydroxide that have not been secondary aggregated are excessively pulverized, thereby impairing the filling of the active material into the electrode substrate due to excessive pulverization, resulting in loss of the active material, Heat generation due to friction of the powder increases, which can prevent the adverse effects such as deterioration of the nickel hydroxide and deterioration of the overelectrode performance.Thus, the prepared mixture powder has an increased bulk density, It is possible to improve the filling property when filling the porous electrode substrate as a paste, and to produce a high-performance paste-type nickel electrode plate with no loss in filling and an increased capacity density.

【００１０】このようにして混合物の粉砕混和処理を行
った後、その調製された混合物粉体を外部に取り出し、
混練機に投入し、これにＣＭＣなどの増粘剤と水などの
溶媒の適量を添加し、混練してペースト状とする。次
で、得られたペースト状混合物を電極基板に、一般に
は、好ましくは、三次元の網状構造をもつ例えば発泡ニ
ッケルシートに充填し、乾燥、プレスして本発明のペー
スト式ニッケル極板の製造を完了する。After the mixture is pulverized and mixed as described above, the prepared mixture powder is taken out to the outside,
The mixture is put into a kneader, and a thickener such as CMC and an appropriate amount of a solvent such as water are added thereto and kneaded to form a paste. Next, the obtained paste-like mixture is filled into an electrode substrate, generally, preferably, for example, into a foamed nickel sheet having a three-dimensional network structure, dried, and pressed to produce the paste-type nickel electrode plate of the present invention. Complete.

【００１１】実施例 約１％のコバルトを固溶した水酸化ニッケル活物質粉末
１０Ｋｇと一酸化コバルト粉末０．８Ｋｇ（水酸化ニッ
ケルに対し８重量％）との混合物を、上記の図示した構
成のフレットミル（皿状うす座の直径は４００ｍｍ、一
対のローラの各ローラの寸法は直径２００ｍｍ×幅１０
０ｍｍ）を用いて粉砕混和処理した。即ち、その混合物
１０．８Ｋｇを該皿状うす座に投入し、回転軸の回転数
を４０ｒｐｍの一定とし、１５分、３０分、６０分、１
２０分、１８０分、２４０分、３６０分と時間を変えて
粉砕混和処理を行い、７種類の混合物粉体を調製した。
その後、夫々得られた混合物粉体ａ，ｂ，ｃ，ｄ，ｅ，
ｆ，ｇを混練機により該混合物粉体に対し増粘剤として
ＣＭＣの１％水溶液４２００ｍｌを添加混練して粘度１
０〜２０Ｐａ・ｓのペースト状とし、その夫々のペース
ト状混合物をスポンジ状ニッケルシートから成る電極基
板に充填し、以下常法により乾燥、プレスして７種類の
ペースト式ニッケル極板Ａ、Ｂ、Ｃ、Ｄ、Ｅ、Ｆ、Ｇを
製造した。比較例として、従来の製造法によって、前記
と同じ原料である水酸化ニッケル活物質粉末１０Ｋｇに
対し前記と同じ原料である一酸化コバルトの添加量を夫
々８重量％及び１２重量％を夫々添加、混合して２種類
の混合物粉体を調製し、その夫々の混合物粉体に前記と
同じＣＭＣ水溶液を同じ量添加混練してペースト状と
し、その夫々を、上記と同じスポンジ状ニッケルシート
から成る電極基板に充填し、同様に乾燥、プレスしてニ
ッケル極板Ｌ、Ｍを製造した。EXAMPLE A mixture of 10 kg of a nickel hydroxide active material powder containing about 1% of solid solution of cobalt and 0.8 kg of cobalt monoxide powder (8% by weight based on nickel hydroxide) was mixed with the above-mentioned structure. Fret mill (Dish-shaped conifer has a diameter of 400 mm, and each roller of the pair of rollers has a diameter of 200 mm x a width of 10 mm.
0 mm). That is, 10.8 kg of the mixture was charged into the dish, and the rotation speed of the rotating shaft was kept constant at 40 rpm, and the mixture was used for 15 minutes, 30 minutes, 60 minutes, and 1 minute.
The pulverization-mixing treatment was performed for 20 minutes, 180 minutes, 240 minutes, and 360 minutes while changing the time, thereby preparing seven types of mixed powders.
Thereafter, the obtained mixture powders a, b, c, d, e,
f and g were added to the mixture powder by a kneader, and 4200 ml of a 1% aqueous solution of CMC was added as a thickener and kneaded to obtain a viscosity of 1%.
A paste of 0 to 20 Pa · s was prepared, and each paste mixture was filled in an electrode substrate formed of a sponge-like nickel sheet, and then dried and pressed by a conventional method to obtain seven types of paste-type nickel electrode plates A, B, C, D, E, F and G were produced. As a comparative example, the same amount of cobalt monoxide as the above-mentioned raw material was added to 10 kg of nickel hydroxide active material powder as the above-mentioned raw material by a conventional manufacturing method, and 8 wt% and 12 wt% of the same raw material were added, Mixing to prepare two kinds of mixture powder, adding the same amount of the same CMC aqueous solution as described above to each mixture powder and kneading them to form pastes, each of which is made of the same sponge-like nickel sheet as described above. The substrate was filled, dried and pressed in the same manner to produce nickel plates L and M.

【００１２】上記のようにして調製した夫々の混合物ａ
〜ｋのかさ密度を、ＪＩＳ Ｋ ５１０１により測定し
た。その結果を下記表１及び図５に示す。Each mixture a prepared as described above
The bulk density of ｋk was measured according to JIS K 5101. The results are shown in Table 1 below and FIG.

【００１３】[0013]

【表１】 [Table 1]

【００１４】上記表１及び図５から明らかなように、回
転軸の回転数、即ち、ローラの回転数４０ｒｐｍで粉砕
混和処理した場合、かさ密度はその処理時間１５分から
１２０分まではその時間経過と共に次第に大きくなり１
２０分で最大となり、２４０分までその最大密度を実質
上一定の値に保持した。このように、かさ密度が時間と
共に大きくなり且つある時間で安定するのは、一酸化コ
バルトの二次凝集体の一次粒子への崩壊が進行して一次
粒子が増量し、且つ水酸化ニッケル粒子間にその微粒子
が均一に分散し、かゝる崩壊作用と混和作用が繰り返さ
れて、遂には、二次凝集体が全く乃至殆どなくなるため
である。その後混合の進行と共に、かさ密度はほんの僅
かづつ小さくなるが、かさ密度１．３８ｇ・ｃｍ-3の近
傍を維持していた。因みに、本発明の粉砕混和処理をし
ない従来の混合物粉体のかさ密度ｇ・ｃｍ-3は、１．２
６ｇ／ｃｍ3 であった。As is apparent from Table 1 and FIG. 5, when the pulverization and mixing treatment is performed at the rotation speed of the rotating shaft, that is, at the rotation speed of the roller of 40 rpm, the bulk density is not changed from 15 minutes to 120 minutes. It gradually grows with 1
It peaked at 20 minutes and held its maximum density at a substantially constant value until 240 minutes. As described above, the bulk density increases with time and stabilizes for a certain time because the collapse of the secondary agglomerate of cobalt monoxide into primary particles progresses, the primary particles increase, and the inter-nickel hydroxide particles This is because the fine particles are uniformly dispersed, and the disintegration action and the mixing action are repeated, so that the secondary aggregates are completely or almost completely eliminated. Thereafter, as the mixing progressed, the bulk density slightly decreased, but the bulk density was maintained at around 1.38 g · cm −3 . By the way, the bulk density g · cm −3 of the conventional mixture powder not subjected to the pulverization mixing treatment of the present invention is 1.2.
It was 6 g / cm 3 .

【００１５】また、上記の本発明により製造した本発明
の極板Ａ〜Ｇ及び従来法で製造した極板Ｌ、Ｍを正極と
し、水素吸蔵電極を負極として組み立て製造したＮｉ−
ＭＨ電池について、所定の充放電試験を行い、夫々の電
池の正極の水酸化ニッケル活物質の利用率及び極板の体
積容量密度を測定した。その結果を下記表２に示す。Further, the Ni-Ag fabricated by assembling and manufacturing the electrode plates A to G of the present invention manufactured according to the present invention and the electrode plates L and M manufactured by the conventional method as positive electrodes and the hydrogen storage electrode as a negative electrode.
For the MH batteries, a predetermined charge / discharge test was performed, and the utilization rate of the nickel hydroxide active material of the positive electrode of each battery and the volume capacity density of the electrode plate were measured. The results are shown in Table 2 below.

【００１６】[0016]

【表２】 [Table 2]

【００１７】上記表２に見られるように、水酸化ニッケ
ル活物質に対するコバルト酸化物の添加量が同じ場合で
も、本発明の粉砕混和処理を経て製造した極板Ａ〜Ｇ
は、かゝる処理を施さない従来法により得た極板Ｌに比
し、その活物質の利用率及び容量密度が略同等又はそれ
以上に向上し、本発明の粉砕混和処理時間が長いほどこ
れらの値が増大することが認められた。As can be seen from Table 2, even when the amount of cobalt oxide added to the nickel hydroxide active material is the same, the plates A to G manufactured through the pulverization and mixing treatment of the present invention are used.
As compared with the electrode plate L obtained by the conventional method without performing such treatment, the utilization factor and the capacity density of the active material are improved to be substantially equal or more, and the longer the pulverization mixing time of the present invention is, It was observed that these values increased.

【００１８】尚、上記の回転軸の回転数を５０ｒ．ｐ．
ｍ．を越えると、水酸化ニッケル粉末を過剰に微粉砕さ
れてかさ密度は小さくなり、そのペースト状混合物の多
孔基板への充填性が劣り、また、摩擦による発熱が生
じ、活物質が変質し、電池性能が低下することが判っ
た。It is to be noted that the rotation speed of the rotating shaft is set to 50 r. p.
m. Is exceeded, the nickel hydroxide powder is excessively pulverized and the bulk density is reduced, the filling property of the paste-like mixture into the porous substrate is inferior, and heat is generated by friction, the active material is deteriorated, and the battery is deteriorated. It was found that the performance decreased.

【００１９】[0019]

【発明の効果】このように本発明によるときは、水酸化
ニッケル粉末にコバルト酸化物粉末との混合物粉体を、
ペースト状として多孔基板に充填する前に、粉砕混和処
理を施してコバルト酸化物の二次凝集体の崩壊とそのほ
ぐれたコバルト酸化物微粒子の水酸化ニッケル粉末中へ
の分散を行った後、この粉砕混和処理済みの混和物粉体
を粘稠性液と共に混練してペースト状とし、次でこれを
多孔性電極基板に充填し、ペースト式ニッケル極板とし
たので、コバルト酸化物の添加量を少なくしても、従来
のペースト式ニッケル極板に比し活物質の利用率並びに
体積容量密度において同等又はそれより高いアルカリ蓄
電池用ペースト式ニッケル極板を得られると共に、従来
に比し経済的に製造することができるなどの効果をもた
らす。この場合、粉砕混和機を用い、好ましくは請求項
３に係る構成のフレットミルを用いて上記混合物の粉砕
混和処理を行い、粉砕混和物が得られ、その回転軸の回
転を５０ｒｐｍ以下とすることにより、水酸化ニッケル
粉末を過剰に粉砕することなく基板に対する充填性に優
れ且つ容量密度の向上した極板を得るに適した粉砕混和
処理物が得られる。As described above, according to the present invention, a mixture powder of nickel hydroxide powder and cobalt oxide powder is used.
Before filling into a porous substrate as a paste, after pulverization and mixing treatment is performed to disintegrate the secondary aggregates of cobalt oxide and disperse the loosened cobalt oxide fine particles in nickel hydroxide powder, The kneaded mixed powder was kneaded with a viscous liquid to form a paste, which was then filled in a porous electrode substrate to form a paste-type nickel electrode plate. Even if it is less, it is possible to obtain a paste-type nickel electrode plate for an alkaline storage battery that is equal to or higher in the utilization factor and the volume capacity density of the active material than the conventional paste-type nickel electrode plate, and is more economical than the conventional one. It has effects such as being able to be manufactured. In this case, the mixture is pulverized and mixed, preferably using a fret mill having the configuration according to claim 3 to obtain a pulverized admixture, and the rotation of the rotation shaft thereof is set to 50 rpm or less. As a result, a pulverized and mixed product suitable for obtaining an electrode plate having an excellent filling property to the substrate and an improved capacity density without excessively pulverizing the nickel hydroxide powder can be obtained.

【図面の簡単な説明】[Brief description of the drawings]

【図１】 本発明のペースト式ニッケル極板の製造法に
用いる粉砕混和機の１例の平面図。FIG. 1 is a plan view of one example of a pulverizer used in the method for producing a paste-type nickel electrode plate of the present invention.

【図２】 図１のＩＩ−ＩＩ線裁断面図。FIG. 2 is a sectional view taken along line II-II of FIG.

【図３】 図１のＩＩＩ−ＩＩＩ線裁断面図。FIG. 3 is a sectional view taken along line III-III of FIG.

【図４】 該粉砕混和機の作動状態を示す一部を裁除し
た拡大側面図。FIG. 4 is an enlarged side view in which an operation state of the pulverizer is partially cut away.

【図５】 ロールミルによる粉砕混和処理時間による混
和物のかさ密度に与える影響を示すグラフ。FIG. 5 is a graph showing the effect on the bulk density of the admixture by the time of the pulverization admixture treatment by a roll mill.

【符号の説明】[Explanation of symbols]

１ 皿状うす座 １ａ 底板 １ｂ 周側壁 ２ 回転軸 ８ａ，８ｂ 一対のローラ支持軸 ９ａ，９ｂ 一
対のローラ １１ａ，１１ｂ 羽根支持部材 １２ａ，１２ｂ
一対の羽根板REFERENCE SIGNS LIST 1 dish-shaped seat 1a bottom plate 1b peripheral wall 2 rotating shaft 8a, 8b pair of roller support shafts 9a, 9b pair of rollers 11a, 11b blade support members 12a, 12b
A pair of slats

Claims (4)

【特許請求の範囲】[Claims] 【請求項１】 水酸化ニッケル活物質粉末とコバルト酸
化物粉末との混合物粉体に粉砕、混和処理を施すことに
より、コバルト酸化物の二次凝集体の凝集をほぐすと共
にほぐれたコバルト酸化物微粉末を該活物質粉末中に均
一に分散混和せしめた混合物粉体を調製した後、この混
合物粉体を増粘剤及び溶媒と共に混練してペースト状と
し、このペースト状混合物を多孔性シートから成る電極
基板に充填することを特徴とするアルカリ蓄電池用ペー
スト式ニッケル極板の製造法。A powder mixture of a nickel hydroxide active material powder and a cobalt oxide powder is pulverized and mixed to disperse the secondary aggregates of the cobalt oxide and disperse the cobalt oxide fine particles. After preparing a mixture powder in which the powder is uniformly dispersed and mixed in the active material powder, the mixture powder is kneaded with a thickener and a solvent to form a paste, and the paste mixture is formed of a porous sheet. A method for producing a paste-type nickel electrode plate for an alkaline storage battery, comprising filling an electrode substrate. 【請求項２】 前記の水酸化ニッケル活物質粉末とコバ
ルト酸化物粉末との混合物粉体に粉砕混和処理を施す工
程は、粉砕混和機を用いて行うことを特徴とする請求項
１記載のアルカリ蓄電池用ペースト式ニッケル極板の製
造法。2. The process according to claim 1, wherein the step of pulverizing and mixing the mixture powder of the nickel hydroxide active material powder and the cobalt oxide powder is performed using a pulverizer. A method for producing a paste-type nickel electrode for a storage battery. 【請求項３】 該粉砕混和機は、水酸化ニッケル活物質
粉末とコバルト酸化物粉末の混合物粉体を収容する皿状
うす座と、該皿状うす座の中心にその底板を貫通して垂
直に取り付けられた回転軸と、該回転軸に一体に取り付
けられた固定保持部材と、該固定保持部材の左右に水平
に配設された一対のローラ支持軸と、該一対のローラ支
持軸に回転自在に且つ該皿状うす座の底面との間に僅か
な間隙を存して取り付けられた一対のローラと、該固定
保持部材の前後に水平に取り付けられた一対の羽根支持
部材と該一対の羽根支持部材の外端部に下端が該皿状う
す座の底面に摺接自在に取り付けられた一対の羽根板と
から構成されるフレットミルである請求項２記載のアル
カリ蓄電池用ペースト式ニッケル極板の製造法。3. The pulverizer includes a dish-shaped seat for containing a mixture powder of a nickel hydroxide active material powder and a cobalt oxide powder, and a vertical plate penetrating a bottom plate at the center of the dish-shaped seat. A rotating shaft attached to the rotating shaft, a fixed holding member integrally attached to the rotating shaft, a pair of roller supporting shafts horizontally disposed on the left and right sides of the fixed holding member, and a pair of rotating shafts. A pair of rollers freely and with a slight gap between the bottom surface of the plate-shaped seat, a pair of blade support members horizontally mounted before and after the fixed holding member, and the pair of blades; 3. A paste-type nickel electrode for an alkaline storage battery according to claim 2, wherein said fret mill comprises a pair of blade plates, the lower end of which is slidably attached to the bottom surface of said dish-shaped seat, at the outer end of said blade support member. The method of manufacturing the board. 【請求項４】 該フレットミルの回転軸の回転速度は、
５０ｒｐｍ以下であることを特徴とする請求項３記載の
アルカリ蓄電池用ペースト式ニッケル極板の製造法。4. The rotation speed of the rotation shaft of the fret mill is:
4. The method for producing a paste-type nickel electrode plate for an alkaline storage battery according to claim 3, wherein the rotation speed is 50 rpm or less.
JP9136027A 1997-05-09 1997-05-09 Manufacture of nickel paste electrode for alkaline storage battery Pending JPH10312799A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP9136027A JPH10312799A (en) 1997-05-09 1997-05-09 Manufacture of nickel paste electrode for alkaline storage battery

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP9136027A JPH10312799A (en) 1997-05-09 1997-05-09 Manufacture of nickel paste electrode for alkaline storage battery

Publications (1)

Publication Number Publication Date
JPH10312799A true JPH10312799A (en) 1998-11-24

Family

ID=15165482

Family Applications (1)

Application Number Title Priority Date Filing Date
JP9136027A Pending JPH10312799A (en) 1997-05-09 1997-05-09 Manufacture of nickel paste electrode for alkaline storage battery

Country Status (1)

Country Link
JP (1) JPH10312799A (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113413796A (en) * 2021-07-12 2021-09-21 吉祥三宝高科纺织有限公司 Dispersion compounding device of PTFE (Polytetrafluoroethylene) particles and additive compound

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113413796A (en) * 2021-07-12 2021-09-21 吉祥三宝高科纺织有限公司 Dispersion compounding device of PTFE (Polytetrafluoroethylene) particles and additive compound
CN113413796B (en) * 2021-07-12 2023-09-19 吉祥三宝高科纺织有限公司 PTFE particle and additive compound's dispersion compounding device

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